Catalyst systems, method for preparing and using same in a polymerization process

ABSTRACT

A polymerization catalyst system and process, which utilizes a Group 14 and Group 16 containing non-crystalline compound to solubilize or emulsify polymerization catalyst components, is disclosed.

CROSS-REFERENCE TO RELATED APPLICATION

[0001] The present application is a Continuation of U.S. Ser. No.10/360,121 filed Feb. 7, 2003, which is a Divisional of, and claimspriority to, U.S. Ser. No. 09/458,399 filed Dec. 10, 1999, now issued asU.S. Pat. No. 6,552,137.

FIELD OF THE INVENTION

[0002] The present invention relates to catalyst systems and to catalystsystem components solubilized or emulsified in a Group 14 and Group 16containing oil or amorphous solid, and to their use in polymerizationprocesses. In a particular, preferred embodiment, the invention isdirected to catalyst systems and components solubilized or emulsifiedwith one or more siloxanes and to methods for preparing and using thesame.

BACKGROUND OF THE INVENTION

[0003] Developments in polymerization technology have provided moreefficient, highly productive and economically enhanced catalyst systemsand processes. Especially illustrative of these advances is thedevelopment of bulky ligand metallocene-type catalysts and of Group 15metal containing catalysts. To utilize these systems in industrialslurry or gas phases processes, it is useful that they be immobilized ona carrier or support such as, for example silica or alumina. Bulkyligand metallocene-type catalysts, however, typically exhibit loweractivity when supported than in the corresponding homogeneous ornon-supported catalyst systems. This “support effect” is especiallydramatic when the catalyst system utilizes a stoichiometric activator,for example a bulky ligand metallocene-type/non-coordinating anioncatalyst system.

[0004] In a typical method to prepare a supported catalyst system, thecatalyst and activator are combined in a suitable solvent then added tothe support or carrier material. However, systems utilizingstoichiometric activators are often difficult to dissolve in hydrocarbonsolvents and as a result are difficult to combine with a supportmaterial. Thus, there is a need to improve the solubility of catalystcompounds, especially those utilizing stoichiometric activators, tofacilitate the preparation of supported catalysts, and also to reducethe “support effect” when using such catalyst systems.

[0005] U.S. Pat. No. 5,747,404 discloses a polysiloxane supportedmetallocene catalyst where the metallocene-type organometallic catalystis directly bonded to a silicon atom in a siloxane polymeric oil.

[0006] PCT WO 99/14269 discloses organopolysiloxane microgel particles,having a diameter of 5 to 200 nm, with organo-aluminum compoundsimmobilized thereon, which may be used as cocatalyst with metalcompounds of the IV, V, VI and VIII sub-groups of the periodic table,for oligomerization cyclization or polymerization of olefins.

[0007] While these catalyst systems and methods have been described inthe art, a need exists for an improved catalyst system and method forpreparing it.

SUMMARY OF THE INVENTION

[0008] This invention provides a new and improved catalyst system, whichinclude a polymerization catalyst combined with a Group 14 and Group 16atom containing oil or amorphous solid. Preferably, the oil or amorphoussolid contains alternating atoms of silicon or germanium and oxygen andmost preferably, the oil or amorphous solid is a siloxane.

[0009] In another embodiment, the invention is directed to a catalystsystem including a polymerization catalyst and an activator, or anactivated polymerization catalyst, combined with a Group 14 and Group 16atom containing oil or amorphous solid.

[0010] In another embodiment the invention relates to a catalyst systemincluding a polymerization catalysts and a stoichiometric activatorcombined with a Group 14 and Group 16 atom containing oil or amorphoussolid, where preferably, the oil or amorphous solid contains alternatingatoms of silicon or germanium and oxygen.

[0011] In another aspect, the invention is directed to a catalyst systemwhich includes a polymerization catalyst and activator combined with apolysiloxane microgel.

[0012] In another aspect the invention relates to a method for making acatalyst system which includes solubilizing or emulsifying apolymerization catalyst and/or an activator in one or more Group 14 andGroup 16 atom containing oil(s) or amorphous solid(s). Optionally, themethod includes further solubilizing the solution or emulsion in ahydrocarbon solvent then combining the resulting solution with a supportor carrier.

[0013] In another aspect, the invention is directed to a polymerizationprocess utilizing a catalyst system of the invention.

[0014] In another aspect, the invention is directed topre-polymerization process utilizing a catalyst system of the invention.

DETAILED DESCRIPTION OF THE INVENTION

[0015] Introduction

[0016] The invention is directed toward a polymerization catalystsystem, which includes a polymerization catalyst combined with a Group14 and Group 16 atom containing oil or amorphous solid. Preferably, theoil or amorphous solid includes alternating atoms of silicon orgermanium, and oxygen. Most preferably, the oil or amorphous solid is asiloxane or a polysiloxane, including microgels. The Group 14 and Group16 atom containing oil or amorphous solid is used to solublize oremulsify the polymerization catalyst and/or the catalyst activator. Ithas been surprisingly discovered that these catalyst solutions oremulsions are highly active especially when a stoichiometric activatoris utilized. The polymerization catalyst systems of the invention may beused in solution, slurry, high pressure or gas phase polymerizationprocesses.

[0017] Polymerization Catalyst

[0018] Bulky Ligand Metallocene-Type Catalyst Compounds

[0019] The Group 14 and Group 16 atom containing oil or amorphous solidmay be used to create solutions or emulsions of the bulky ligandmetallocene-type polymerization catalysts described below. Generally,these catalyst compounds include half and full sandwich compounds havingone or more bulky ligands bonded to at least one metal atom. Typicalbulky ligand metallocene-type compounds are described as containing oneor more bulky ligand(s) and one or more leaving group(s) bonded to atleast one metal atom. In one preferred embodiment, at least one bulkyligands is η-bonded to the metal atom, most preferably η⁵-bonded to atransition metal atom.

[0020] The bulky ligands are generally represented by one or more open,acyclic, or fused ring(s) or ring system(s) or a combination thereof.The ring(s) or ring system(s) of these bulky ligands are typicallycomposed of atoms selected from Groups 13 to 16 atoms of the PeriodicTable of Elements. Preferably the atoms are selected from the groupconsisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorous,germanium, boron and aluminum or a combination thereof. Most preferablythe ring(s) or ring system(s) are composed of carbon atoms such as butnot limited to those cyclopentadienyl ligands or cyclopentadienyl-typeligand structures or other similar functioning ligand structure such asa pentadiene, a cyclooctatetraendiyl or an imide ligand. The metal atomis preferably selected from Groups 3 through 15 and the lanthamide oractinide series of the Periodic Table of Elements. Preferably the metalis a transition metal from Groups 4 through 12, more preferably Groups4, 5 and 6, and most preferably the transition metal is from Group 4.

[0021] In one embodiment, the Group 14 and Group 16 atom containingnon-crystalline compound may be used to create solutions or emulsions ofthe bulky ligand metallocene-type catalyst compounds represented by theformula:

[0022] L^(A)L^(B)MQ_(n)  (I)

[0023] where M is a metal atom from the Periodic Table of the Elementsand may be a Group 3 to 12 metal or from the lanthamide or actinideseries of the Periodic Table of Elements, preferably M is a Group 4, 5or 6 transition metal, more preferably M is zirconium, hafuium ortitanium. The bulky ligands, L^(A) and L^(B), are open, acyclic or fusedring(s) or ring system(s) and are any ancillary ligand system, includingunsubstituted or substituted, cyclopentadienyl ligands orcyclopentadienyl-type ligands, heteroatom substituted and/or heteroatomcontaining cyclopentadienyl-type ligands. Non-limiting examples of bulkyligands include cyclopentadienyl ligands, cyclopentaphenanthreneylligands, indenyl ligands, benzindenyl ligands, fluorenyl ligands,octahydrofluorenyl ligands, cyclooctatetraendiyl ligands,cyclopentacyclododecene ligands, azenyl ligands, azulene ligands,pentalene ligands, phosphoyl ligands, phosphinimine (WO 99/40125),pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzeneligands and the like, including hydrogenated versions thereof, forexample tetrahydroindenyl ligands. In one embodiment, L^(A) and L^(B)may be any other ligand structure capable of η-bonding to M, preferablyη³-bonding to M and most preferably η⁵-bonding. In yet anotherembodiment, the atomic molecular weight (MW) of L^(A) or L^(B) exceeds60 a.m.u., preferably greater than 65 a.m.u. In another embodiment,L^(A) and L^(B) may comprise one or more heteroatoms, for example,nitrogen, silicon, boron, germanium, sulfur and phosphorous, incombination with carbon atoms to form an open, acyclic, or preferably afused, ring or ring system, for example, a hetero-cyclopentadienylancillary ligand. Other L^(A) and L^(B) bulky ligands include but arenot limited to bulky amides, phosphides, alkoxides, aryloxides, imides,carbolides, borollides, porphyrins, phthalocyanines, corrins and otherpolyazomacrocycles. Independently, each L^(A) and L^(B) may be the sameor different type of bulky ligand that is bonded to M. In one embodimentof formula (I) only one of either L^(A) or L^(B) is present.

[0024] Independently, each L^(A) and L^(B) may be unsubstituted orsubstituted with a combination of substituent groups R. Non-limitingexamples of substituent groups R include one or more from the groupselected from hydrogen, or linear, branched alkyl radicals, or alkenylradicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acylradicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthioradicals, dialkylamino radicals, alkoxycarbonyl radicals,aryloxycarbonyl radicals, carbomoyl radicals, alkyl- or dialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals, aroylaminoradicals, straight, branched or cyclic, alkylene radicals, orcombination thereof. In a preferred embodiment, substituent groups Rhave up to 50 non-hydrogen atoms, preferably from 1 to 30 carbon, thatcan also be substituted with halogens or heteroatoms or the like.Non-limiting examples of alkyl substituents R include methyl, ethyl,propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenylgroups and the like, including all their isomers, for example tertiarybutyl, isopropyl, and the like. Other hydrocarbyl radicals includefluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl,chlorobenzyl and hydrocarbyl substituted organometalloid radicalsincluding trimethylsilyl, trimethylgermyl, methyldiethylsilyl and thelike; and halocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)-silyl, methyl-bis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstitiuted boronradicals including dimethylboron for example; and disubstitutedpnictogen radicals including dimethylamine, dimethylphosphine,diphenylamine, methylphenylphosphine, chalcogen radicals includingmethoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide.Non-hydrogen substituents R include the atoms carbon, silicon, boron,aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium and thelike, including olefins such as but not limited to olefinicallyunsaturated substituents including vinyl-terminated ligands, for examplebut-3-enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least two Rgroups, preferably two adjacent R groups, are joined to form a ringstructure having from 3 to 30 atoms selected from carbon, nitrogen,oxygen, phosphorous, silicon, germanium, aluminum, boron or acombination thereof. Also, a substituent group R group such as 1-butanylmay form a carbon sigma bond to the metal M.

[0025] Other ligands may be bonded to the metal M, such as at least oneleaving group Q. For the purposes of this patent specification andappended claims the term “leaving group” is any ligand that can beabstracted from a bulky ligand metallocene-type catalyst compound toform a bulky ligand metallocene-type catalyst cation capable ofpolymerizing one or more olefin(s). In one embodiment, Q is amonoanionic labile ligand having a sigma-bond to M. Depending on theoxidation state of the metal, the value for n is 0, 1 or 2 such thatformula (I) above represents a neutral bulky ligand metallocene-typecatalyst compound.

[0026] Non-limiting examples of Q ligands include weak bases such asamines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicalshaving from 1 to 20 carbon atoms, hydrides or halogens and the like or acombination thereof. In another embodiment, two or more Q's form a partof a fused ring or ring system. Other examples of Q ligands includethose substituents for R as described above and including cyclobutyl,cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene,pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy,bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and thelike.

[0027] In another embodiment, the Group 14 and Group 16 atom containingnon-crystalline compound may be used to create solutions or emulsions ofthe bulky ligand metallocene-type catalyst compounds of formula (I)where L^(A) and L^(B) are bridged to each other by at least one bridginggroup, A, as represented in the following formula:

L^(A)AL^(B)MN_(n)  (II)

[0028] These bridged compounds represented by formula (II) are known asbridged, bulky ligand metallocene-type catalyst compounds. L^(A), L^(B),M, Q and n are as defined above. Non-limiting examples of bridging groupA include bridging groups containing at least one Group 13 to 16 atom,often referred to as a divalent moiety such as but not limited to atleast one of a carbon, oxygen, nitrogen, silicon, aluminum, boron,germanium and tin atom or a combination thereof. Preferably bridginggroup A contains a carbon, silicon or germanium atom, most preferably Acontains at least one silicon atom or at least one carbon atom. Thebridging group A may also contain substituent groups R as defined aboveincluding halogens and iron. Non-limiting examples of bridging group Amay be represented by R′₂C, R′₂Si, R′₂Si R′₂Si, R′₂Ge, R′P, where R′ isindependently, a radical group which is hydride, hydrocarbyl,substituted hydrocarbyl, halocarbyl, substituted halocarbyl,hydrocarbyl-substituted organometalloid, halocarbyl-substitutedorganometalloid, disubstituted boron, disubstituted pnictogen,substituted chalcogen, or halogen or two or more R′ may be joined toform a ring or ring system. In one embodiment, the bridged, bulky ligandmetallocene-type catalyst compounds of formula (II) have two or morebridging groups A (EP 664 301 B 1).

[0029] In one embodiment, the bulky ligand metallocene-type catalystcompounds are those where the R substituents on the bulky ligands L^(A)and L^(B) of formulas (1) and (II) are substituted with the same ordifferent number of substituents on each of the bulky ligands. Inanother embodiment, the bulky ligands LA and LBof formulas (I) and (II)are different from each other.

[0030] Other bulky ligand metallocene-type catalyst compounds andcatalyst systems useful in the invention may include those described inU.S. Pat. Nos. 5,064,802, 5,145,819, 5,149,819, 5,243,001, 5,239,022,5,276,208, 5,296,434, 5,321,106, 5,329,031, 5,304,614, 5,677,401,5,723,398, 5,753,578, 5,854,363, 5,856,547 5,858,903, 5,859,158,5,900,517 and 5,939,503 and PCT publications WO 93/08221, WO 93/08199,WO 95/07140, WO 98/11144, WO 98/41530, WO 98/41529, WO 98/46650, WO99/02540 and WO 99/14221 and European publications EP-A-0 578 838,EP-A-0 638 595, EP-B-0 513 380, EP-A1-0 816 372, EP-A2-0 839 834,EP-B1-0 632 819, EP-B1-0 748 821 and EP-B 1-0 757 996, all of which areherein fully incorporated by reference.

[0031] In one embodiment, bulky ligand metallocene-type catalystscompounds useful in the invention include bridged heteroatom, mono-bulkyligand metallocene-type compounds. These types of catalysts and catalystsystems are described in, for example, PCT publication WO 92/00333, WO94/07928, WO 91/04257, WO 94/03506, WO96/00244, WO 97/15602 and WO99/20637 and U.S. Pat. Nos. 5,057,475, 5,096,867, 5,055,438, 5,198,401,5,227,440 and 5,264,405 and European publication EP-A-0 420 436, all ofwhich are herein fully incorporated by reference.

[0032] In this embodiment, the bulky ligand metallocene-type catalystcompound is represented by the formula:

L^(C)AJMQ_(n)  (III)

[0033] where M is a Group 3 to 16 metal atom or a metal selected fromthe Group of actinides and lanthamides of the Periodic Table ofElements, preferably M is a Group 4 to 12 transition metal, and morepreferably M is a Group 4, 5 or 6 transition metal, and most preferablyM is a Group 4 transition metal in any oxidation state, especiallytitanium; L^(C) is a substituted or unsubstituted bulky ligand bonded toM; J is bonded to M; A is bonded to M and J; J is a heteroatom ancillaryligand; and A is a bridging group; Q is a univalent anionic ligand; andn is the integer 0, 1 or 2. In formula (im) above, L^(C), A and J form afused ring system. In an embodiment, L^(C) of formula (III) is asdefined above for L^(A), A, M and Q of formula (III) are as definedabove in formula (I).

[0034] In formula (III) J is a heteroatom containing ligand in which Jis an element with a coordination number of three from Group 15 or anelement with a coordination number of two from Group 16 of the PeriodicTable of Elements. Preferably J contains a nitrogen, phosphorus, oxygenor sulfur atom with nitrogen being most preferred.

[0035] In another embodiment, the bulky ligand type metallocene-typecatalyst compound is a complex of a metal, preferably a transitionmetal, a bulky ligand, preferably a substituted or unsubstitutedpi-bonded ligand, and one or more heteroallyl moieties, such as thosedescribed in U.S. Pat. Nos. 5,527,752 and 5,747,406 and EP-B1-0 735 057,all of which are herein fully incorporated by reference.

[0036] In an embodiment, the Group 14 and Group 16 atom containingnon-crystalline compound may be used to create solutions or emulsions ofthe bulky ligand metallocene-type catalyst compounds represented by theformula:

L^(D)MQ₂(YZ)X_(n)  (IV)

[0037] where M is a Group 3 to 16 metal, preferably a Group 4 to 12transition metal, and most preferably a Group 4, 5 or 6 transitionmetal; LD is a bulky ligand that is bonded to M; each Q is independentlybonded to M and Q₂(YZ) forms a unicharged polydentate ligand; A or Q isa univalent anionic ligand also bonded to M; X is a univalent anionicgroup when n is 2 or X is a divalent anionic group when n is 1; n is 1or 2.

[0038] In formula (IV), L and M are as defined above for formula (I). Qis as defined above for formula (I), preferably Q is selected from thegroup consisting of —O—, —NR—, —CR₂— and —S—; Y is either C or S; Z isselected from the group consisting of —OR, —NR₂, —CR₃, —SR, —SiR₃, —PR₂,—H, and substituted or unsubstituted aryl groups, with the proviso thatwhen Q is —NR— then Z is selected from one of the group consisting of—OR, —NR₂, —SR, —SiR₃, —PR₂ and —H; R is selected from a groupcontaining carbon, silicon, nitrogen, oxygen, and/or phosphorus,preferably where R is a hydrocarbon group containing from 1 to 20 carbonatoms, most preferably an alkyl, cycloalkyl, or an aryl group; n is aninteger from 1 to 4, preferably 1 or 2; X is a univalent anionic groupwhen n is 2 or X is a divalent anionic group when n is 1; preferably Xis a carbamate, carboxylate, or other heteroallyl moiety described bythe Q, Y and Z combination.

[0039] In another embodiment of the invention, the bulky ligandmetallocene-type catalyst compounds are heterocyclic ligand complexeswhere the bulky ligands, the ring(s) or ring system(s), include one ormore heteroatoms or a combination thereof. Non-limiting examples ofheteroatoms include a Group 13 to 16 element, preferably nitrogen,boron, sulfuir, oxygen, aluminum, silicon, phosphorous and tin. Examplesof these bulky ligand metallocene-type catalyst compounds are describedin WO 96/33202, WO 96/34021, WO 97/17379 and WO 98/22486 and EP-A1-0 874005 and U.S. Pat. Nos. 5,637,660, 5,539,124, 5,554,775, 5,756,611,5,233,049, 5,744,417, and 5,856,258 all of which are herein incorporatedby reference.

[0040] In another embodiment, the bulky ligand metallocene-type catalystcompounds are those complexes known as transition metal catalysts basedon bidentate ligands containing pyridine or quinoline moieties, such asthose described in U.S. application Ser. No. 09/103,620 filed Jun. 23,1998, which is herein incorporated by reference. In another embodiment,the bulky ligand metallocene-type catalyst compounds are those describedin PCT publications WO 99/01481 and WO 98/42664, which are fullyincorporated herein by reference.

[0041] In one embodiment, the Group 14 and Group 16 atom containingnon-crystalline compound may be used to create solutions or emulsions ofthe bulky ligand metallocene-type catalyst compounds represented by theformula:

((Z)XA_(t)(YJ))_(q)MQ_(n)  (V)

[0042] where M is a metal selected from Group 3 to 13 or lanthamide andactinide series of the Periodic Table of Elements; Q is bonded to M andeach Q is a monovalent, bivalent, or trivalent anion; X and Y are bondedto M; one or more of X and Y are heteroatoms, preferably both X and Yare heteroatoms; Y is contained in a heterocyclic ring J, where Jcomprises from 2 to 50 non-hydrogen atoms, preferably 2 to 30 carbonatoms; Z is bonded to X, where Z comprises 1 to 50 non-hydrogen atoms,preferably 1 to 50 carbon atoms, preferably Z is a cyclic groupcontaining 3 to 50 atoms, preferably 3 to 30 carbon atoms; t is 0 or 1;when t is 1, A is a bridging group joined to at least one of X, Y or J,preferably X and J; q is 1 or 2; n is an integer from 1 to 4 dependingon the oxidation state of M. In one embodiment, where X is oxygen orsulfur then Z is optional. In another embodiment, where X is nitrogen orphosphorous then Z is present. In an embodiment, Z is preferably an arylgroup, more preferably a substituted aryl group.

[0043] It is also within the scope of this invention, in one embodiment,that the bulky ligand metallocene-type catalyst compounds includecomplexes of Ni²⁺ and Pd²⁺ described in the articles Johnson, et al.,“New Pd(II)— and Ni(II)- Based Catalysts for Polymerization of Ethyleneand a-Olefins”, J. Am. Chem. Soc. 1995, 117, 6414-6415 and Johnson, etal., “Copolymerization of Ethylene and Propylene with FunctionalizedVinyl Monomers by Palladium(II) Catalysts”, J. Am. Chem. Soc., 1996,118, 267-268, and WO 96/23010 published Aug. 1, 1996, WO 99/02472, U.S.Pat. Nos. 5,852,145, 5,866,663 and 5,880,241, which are all herein fullyincorporated by reference. These complexes can be either dialkyl etheradducts, or alkylated reaction products of the described dihalidecomplexes that can be activated to a cationic state by the activators ofthis invention described below.

[0044] Also included as bulky ligand metallocene-type catalyst are thosediimine based ligands of Group 8 to 10 metal compounds disclosed in PCTpublications WO 96/23010 and WO 97/48735 and Gibson, et. al., Chem.Comm., pp. 849-850 (1998), all of which are herein incorporated byreference.

[0045] Other bulky ligand metallocene-type catalysts are those Group 5and 6 metal imido complexes described in EP-A2-0 816 384 and U.S. Pat.No. 5,851,945, which is incorporated herein by reference. In addition,bulky ligand metallocene-type catalysts include bridged bis(arylamido)Group 4 compounds described by D. H. McConville, et al., inOrganometallics 1195, 14, 5478-5480, which is herein incorporated byreference. In addition, bridged bis(amido) catalyst compounds aredescribed in WO 96/27439, which is herein incorporated by reference.Other bulky ligand metallocene-type catalysts are described asbis(hydroxy aromatic nitrogen ligands) in U.S. Pat. No. 5,852,146, whichis incorporated herein by reference. Other metallocene-type catalystscontaining one or more Group 15 atoms include those described in WO98/46651, which is herein incorporated herein by reference. Stillanother metallocene-type bulky ligand metallocene-type catalysts includethose multinuclear bulky ligand metallocene-type catalysts as describedin WO 99/20665, which is incorporated herein by reference.

[0046] It is also contemplated that in one embodiment, the bulky ligandmetallocene-type catalysts of the invention described above includetheir structural or optical or enantiomeric isomers (meso and racemicisomers, for example see U.S. Pat. No. 5,852,143, incorporated herein byreference) and mixtures thereof.

[0047] Group 15 Containing Polymerization Catalyst

[0048] The Group 14 and Group 16 atom containing oil or amorphous solidmay also be used to create solutions or emulsions of Group 15 metalcontaining polymerization catalyst. Generally, these catalysts includesa Group 3 to 14 metal atom, preferably a Group 3 to 7, more preferably aGroup 4 to 6, and even more preferably a Group 4 metal atom, bound to atleast one leaving group and also bound to at least two Group 15 atoms,at least one of which is also bound to a Group 15 or 16 atom throughanother group.

[0049] Preferably, at least one of the Group 15 atoms is also bound to aGroup 15 or 16 atom through another group which may be a C₁ to C₂₀hydrocarbon group, a heteroatom containing group, silicon, germanium,tin, lead, or phosphorus, wherein the Group 15 or 16 atom may also bebound to nothing or a hydrogen, a Group 14 atom containing group, ahalogen, or a heteroatom containing group, and wherein each of the twoGroup 15 atoms are also bound to a cyclic group and may optionally bebound to hydrogen, a halogen, a heteroatom or a hydrocarbyl group, or aheteroatom containing group.

[0050] It is also contemplated that any one of the catalyst compoundsdescribed above may have at least one fluoride or fluorine containingleaving group as described in U.S. application Ser. No. 09/191,916 filedNov. 13, 1998.

[0051] In another embodiment of the invention the composition containingalternating atoms of Group 14 and Group 16 may be used to createsolutions or emulsions including one or more bulky ligandmetallocene-type catalyst compounds, and one or more conventional-typecatalyst compounds or catalyst systems. Non-limiting examples of mixedcatalysts and catalyst systems are described in U.S. Pat. Nos.4,159,965, 4,325,837, 4,701,432, 5,124,418, 5,077,255, 5,183,867,5,391,660, 5,395,810, 5,691,264, 5,723,399 and 5,767,031 and PCTPublication WO 96/23010 published Aug. 1, 1996, all of which are hereinfully incorporated by reference.

[0052] Activator Compositions

[0053] The above described polymerization catalyst compounds aretypically activated in various ways to yield compounds having a vacantcoordination site that will coordinate, insert, and polymerizeolefin(s). The catalyst system of the invention may include an activatoror activators combined with the composition containing alternating atomsof Group 14 and Group 16.

[0054] For the purposes of this patent specification and appendedclaims, the term “activator” is defined to be any compound or componentor method which can activate any of the bulky ligand metallocene-typecatalyst compounds and/or the Group 15 metal containing catalystsdescribed above. Non-limiting activators, for example, may include aLewis acid or a non-coordinating ionic activator or ionizing activatoror any other compound including Lewis bases, aluminum alkyls,conventional-type cocatalysts and combinations thereof that can converta neutral bulky ligand metallocene-type catalyst compound or Group 15containing metal compound to a catalytically active bulky ligandmetallocene-type or Group 15 containing metal compound catalyst cation.

[0055] It is within the scope of this invention to use as alumoxane ormodified alumoxanes as an activator. There are a variety of methods forpreparing alumoxane and modified alumoxanes, non-limiting examples ofwhich are described in U.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352,5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827,5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031,5,391,793, 5,391,529, 5,693,838, 5,731,253, 5,731,451, 5,744,656,5,847,177, 5,854,166, 5,856,256 and 5,939,346 and European publicationsEP-A-0 561 476, EP-B1-0 279 586, EP-A-0 594-218 and EP-B1-0 586 665, andPCT publication WO 94/10180, all of which are herein fully incorporatedby reference.

[0056] In one embodiment aluminoxanes or modified alumoxanes arecombined with catalyst compound(s) solubilized or emulsified in thecomposition containing alternating atoms of Group 14 and Group 16 of theinvention. In another embodiment MMAO3A (modified methyl alumoxane inheptane, commercially available from Akzo Chemicals, Inc., Holland,under the trade name Modified Methylalumoxane type 3A, see for examplethose aluminoxanes disclosed in U.S. Pat. No. 5,041,584, which is hereinincorporated by reference) is combined with the catalyst compound(s) andthe composition containing alternating atoms of Group 14 and Group 16,to form a catalyst system of the invention.

[0057] Organoaluminum compounds useful as activators includetrimethylaluminum, triethylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum and the like.

[0058] It is within the scope of this invention to use an ionizing orstoichiometric activator, neutral or ionic, such as tri (n-butyl)ammonium tetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boronmetalloid precursor or a trisperfluoronaphtyl boron metalloid precursor,polyhalogenated heteroborane anions (WO 98/43983) or combinationthereof, that would ionize the neutral bulky ligand metallocene-typecatalyst and/or the Group 15 containing metal compound. It is alsowithin the scope of this invention to use neutral or ionic activatorsalone or in combination with alumoxane or modified alumoxane activators.

[0059] An example of a neutral stoichiometric activator, which may besolubilized or emulsified by the composition containing alternatingatoms of Group 14 and Group 16, include tri-substituted boron,tellurium, aluminum, gallium and indium or mixtures thereof. The threesubstituent groups are each independently selected from alkyls,alkenyls, halogen, substituted alkyls, aryls arylhalides, alkoxy andhalides. Preferably, the three groups are independently selected fromhalogen, mono or multicyclic (including halosubstituted) aryls, alkyls,and alkenyl compounds and mixtures thereof, preferred are alkenyl groupshaving 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms,alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20carbon atoms (including substituted aryls). More preferably, the threegroups are alkyls having 1 to 4 carbon groups, phenyl, napthyl ormixtures thereof. Most preferably, the neutral stoichiometric activatoris trisperfluorophenyl boron or trisperfluoronapthyl boron.

[0060] In a preferred embodiment, the catalyst system of the inventionincludes an ionic stoichiometric activator solubilized or emulsified bythe composition containing alternating atoms of Group 14 and Groupl6.Ionizing activator compounds may contain an active proton, or some othercation associated with but not coordinated to or only looselycoordinated to the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP-A-0 570982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 andEP-A-0 277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741,5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. patentapplication Ser. No. 08/285,380, filed Aug. 3, 1994, all of which areherein fully incorporated by reference.

[0061] In a preferred embodiment, the stoichiometric activators includea cation and an anion component, and may be represented by the followingformula:

(L-H)d⁺(A^(d−))  (VI)

[0062] wherein L′ is an neutral Lewis base;

[0063] H is hydrogen;

[0064] (L-H)⁺is a Bronsted acid A^(d−) is a non-coordinating anionhaving the charge d−

[0065] d is an integer from 1 to 3.

[0066] The cation component, (L-H)_(d) ⁺ may include Bronsted acids suchas protons or protonated Lewis bases or reducible Lewis acids capable ofprotonating or abstracting a moiety, such as an akyl or aryl, from thebulky ligand metallocene-type or Group 15 containing transition metalcatalyst precursor, resulting in a cationic transition metal species.

[0067] The activating cation (L-H)_(d) ⁺may be a Bronsted acid, capableof donating a proton to the transition metal catalytic precursorresulting in a transition metal cation, including ammoniums, oxoniums,phosphoniums, silyliums and mixtures thereof, preferably ammoniums ofmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such asdimethyl ether diethyl ether, tetrahydroffuran and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene andmixtures thereof. Most preferably, dimethylanaline. The activatingcation (L-H)_(d) ⁺ may also be an abstracting moiety such as silver,carboniums, tropylium, carbeniums, ferroceniums and mixtures, preferablycarboniums and ferroceniums. Most preferably (L-H)_(d)+is triphenylcarbonium.

[0068] The anion component A^(d−) include those having the formula[M^(k+)Q_(n)]^(d−) wherein k is an integer from 1 to 3; n is an integerfrom 2-6; n-k=d; M is an element selected from Group 13 of the PeriodicTable of the Elements and Q is independently a hydride, bridged orunbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl,substituted hydrocarbyl, halocarbyl, substituted halocarbyl, andhalosubstituted-hydrocarbyl radicals, said Q having up to 20 carbonatoms with the proviso that in not more than 1 occurrence is Q a halide.Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 20carbon atoms, more preferably each Q is a fluorinated aryl group, andmost preferably each Q is a pentafluoryl aryl group.

[0069] In a most preferred embodiment, the ionic stoichiometricactivator (L-H)_(d) ⁺ (A^(d−)) is N,N-dimethylaniliniumtetra(perfluorophenyl)borate or triphenylcarbeniumtetra(perfluorophenyl)borate.

[0070] Examples of suitable A^(d−) also include diboron compounds asdisclosed in U.S. Pat. No. 5,447,895, which is fully incorporated hereinby reference.

[0071] In one embodiment, an activation method using ionizing ioniccompounds not containing an active proton but capable of producing aGroup 15 containing metal compound cation or bulky ligandmetallocene-type catalyst cation and their non-coordinating anion arealso contemplated, and are described in EP-A-0 426 637, EP-A-0 573 403and U.S. Pat. No. 5,387,568, which are all herein incorporated byreference.

[0072] Other activators include those described in PCT publication WO98/07515 such as tris (2,2′, 2″-nonafluorobiphenyl) fluoroaluminate,which publication is fully incorporated herein by reference.Combinations of activators are also contemplated by the invention, forexample, alumoxanes and ionizing activators in combinations, see forexample, EP-B1 0 573 120, PCT publications WO 94/07928 and WO 95/14044and U.S. Pat. Nos. 5,153,157 and 5,453,410 all of which are herein fullyincorporated by reference.

[0073] Other suitable activators are disclosed in WO 98/09996,incorporated herein by reference, which describes activating bulkyligand metallocene-type catalyst compounds with perchlorates, periodatesand iodates including their hydrates. WO 98/30602 and WO 98/30603,incorporated by reference, describe the use of lithium(2,2′-bisphenyl-ditrimethylsilicate)·4THF as an activator for a bulkyligand metallocene-type catalyst compound. WO 99/18135, incorporatedherein by reference, describes the use of organo-boron-aluminumacitivators. EP-B 1-0 781 299 describes using a silylium salt incombination with a non-coordinating compatible anion. Also, methods ofactivation such as using radiation (see EP-B 1-0 615 981 hereinincorporated by reference), electro-chemical oxidation, and the like arealso contemplated as activating methods for the purposes of renderingthe neutral bulky ligand metallocene-type catalyst compound or precursorto a bulky ligand metallocene-type cation capable of polymerizingolefins. Other activators or methods for activating a bulky ligandmetallocene-type catalyst compound are described in for example, U.S.Pat. Nos. 5,849,852, 5,859,653 and 5,869,723 and WO 98/32775, WO99/42467 (dioctadecylmethylammonium-bis(tris(pentafluorophenyl)borane)benzimidazolide), which are herein incorporated by reference.

[0074] Group 14 and Group 16 atom Containing Oils or Amorphous Solids

[0075] One or more Group 14 and Group 16 containing oil or amorphoussolid are combined with the above described bulky ligandmetallocene-type catalyst compounds and/or Group 15 metal containingcatalyst compounds and/or activator compositions to form a catalyst, acatalyst activator, or an activated catalyst solution or emulsion.Preferably, the oil or amorphous solid contains alternating atoms ofGroup 14 and Group 16. More preferably, the oil or amorphous solidcontains silicon or germanium and oxygen. More preferably the oil oramorphous solid is a siloxane, polysiloxane or a polysiloxane microgeland most preferably a siloxane. The Group 14 and Group 16 containing oilor amorphous solid, and in particular siloxanes, improve the solubilityof catalyst and/or activators to form catalyst solutions or emulsions ofrelative higher activity, particularly when stoichiometric activatorsare utilized.

[0076] The Group 14 and Group 16 containing oil or amorphous solid areavailable in a wide range of solubility, and may be represented by oneof the general formulae appearing below:

T-M(R¹)₂-Q-(M(R²)₂-Q)_(n)-M(R¹)₂-T  (VII)

T-M(R¹)₂-Q-(M(R²)₂-Q)_(n)-(M(R³)₂-Q)_(m)-M(R¹)₂-T (VIII)

[0077] where each T is independently selected from, hydrogen, an alkyl,alkoxy, aryl, substituted aryl, cycloalkyl, substituted cyclic alkyl,cyclic aralkyl, substituted cyclic aralkyl, heteroatom, vinyl, silyl,silyloxy, vinylsiloxy, hydride, haloaryl, haloalkyl, or vinylsilylcontaining group. Preferably, each T is independently selected from C₁to C₂₀ alkyl or an aryl group. More preferably each T is independently amethyl, ethyl, isopropyl butyl, vinyl or phenyl group, and mostpreferably a methyl, ethyl or vinyl group.

[0078] Each M is independently an atom of Group 14 of the PeriodicTable, preferably M is silicon or germanium, more preferably M issilicon.

[0079] Each Q is independently an atom of Group 16 of the Periodic Tableof the Elements, preferably Q is oxygen.

[0080] Each R¹′ and each R² is independently selected from hydrogen, analkyl, alkoxy, aryl, substituted aryl, cycloalkyl, substituted cyclicalkyl, cyclic aralkyl, substituted cyclic aralkyl, heteroatom, vinyl,silyl, silyloxy, vinylsiloxy, hydride, haloaryl, haloalkyl, orvinylsilyl containing group. Preferably, each R¹ and each R² isindependently selected from an alkyl group having 1 to 20 carbon atomsor an aryl group. More preferably, each R¹ and each R² is independentlya methyl group, an ethyl group, or a haloalkyl. Most preferably, each R¹and each R² is independently a methyl group, an ethyl group, or afluoro-alkyl.

[0081] Each R³ is independently selected from hydrogen, an alkyl,alkoxy, aryl, substituted aryl, cycloalkyl, substituted cyclic alkyl,cyclic aralkyl, substituted cyclic aralkyl, heteroatom, vinyl, silyl,silyloxy, vinylsiloxy, hydride, haloaryl, haloalkyl, or vinylsilylcontaining group. Preferably, each R³ is independently selected from analkyl group having 1 to 20 carbon atoms, a halogenated alkyl group, oran aryl group. Most preferably, R³ is a halogenated or non-halogenatedmethyl, ethyl, propyl or phenyl group.

[0082] n and m are independently 0 or an integer from 1 to 40,000,preferably from 1 to 20,000 and more preferably from 1 and 10,000.

[0083] In one embodiment, the terminal groups T, may be connected, byfor example a heteroatom or by a polysiloxy group to form a cyclicsiloxane.

[0084] The alkyl group, as used above, may be a linear, branched alkylradicals, or alkenyl radicals, alkynyl radicals, cycloalkyl radicals oraryl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxyradicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonylradicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- ordialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,aroylamino radicals, straight, branched or cyclic, alkylene radicals, orcombination thereof. An aralkyl group is defined to be a substitutedaryl group.

[0085] In one embodiment, the composition containing alternating atomsof Group 14 and Group 16 of the invention, preferably a siloxane orcombination of siloxanes, has a viscosity of between about 1 cSt and2,500,000 cSt, more preferably between about 100 cSt and 500,000 cSt,more preferably between about 100 cSt to about 50,000 cSt, and even morepreferably between about 500 and 5000 cSt.

[0086] In one embodiment, the composition containing alternating atomsof Group 14 and Group 16 of the invention, preferably a siloxane orcombination of siloxanes, has a number average molecular weight (M_(n))of between about 40 and 500,000, more preferably between about 60 and100,000 and even more preferably between about 1,000 and 60,000 and mostpreferably between about 5,000 and 40,000.

[0087] In a most preferred embodiment, the composition containingalternating atoms of Group 14 and Group 16 is a vinyl terminateddimethyl methyltrifluoropropylsiloxane with a M_(n) of between about20,000 and about 40,000.

[0088] Preparation of the Catalyst Solution or Emulsion

[0089] The method for making the catalyst solution or emulsion of theinvention generally involves the combining, contacting, blending one ormore of the Group 14 and Group 16 containing oil or amorphous soliddescribed above with any catalyst compounds and/or activator compounds,alone or in combinations. Preferably, the Group 14 and Group 16containing oil or amorphous solid is first purified as is known in theart. Most preferably, the Group 14 and Group 16 containing oil oramorphous solid is a siloxane, or combination of siloxanes, which hasbeen purified, for example, by vacuum drying and/or refluxing in asuitable solvent, for example toluene, as is known in the art.

[0090] In a preferred embodiment, the catalyst solution or emulsion ofthe invention is formed by first combining the catalyst compound and/orthe activator composition with an aliphatic or aromatic hydrocarbon,most preferably toluene, and then combining with the Group 14 and Group16 containing oil or amorphous solid. When a siloxane is utilized, theresulting solution or emulsion is typically yellow or orange in color.

[0091] Optionally, a scavenger, preferably tri-n-octylaluminum, is addedto Group 14 and Group 16 containing oil or amorphous solid, preferablyprior to the addition of the catalyst compound. While not limited to anyone particular theory, it is believed that the addition of a scavengeroperates to remove residual hydroxyl groups and water from the preferredsiloxane.

[0092] In general the catalyst compound(s) and the activator arecombined in the solution or emulsion in mole ratios of catalyst compoundto activator of about 1000:1 to about 0.5:1. In a preferred embodimentthe catalyst compounds and the activator are combined in a mole ratio ofabout 300:1 to about 1:1, and preferably about 150:1 to about 1:1. Forboranes, borates, aluminates, etc. the mole ratio of catalyst toactivator is preferably about 1:1 to about 10:1 and for alkyl aluminumcompounds (such as diethylaluminum chloride combined with water) themole ratio is preferably about 0.5:1 to about 10:1. In a preferredembodiment, an ionizing activator is used and the mole ratio of themetal of the ionizing activator component to the metal of the catalystcompounds between about 0.3:1 to about 3:1.

[0093] Optionally, the catalyst solution or emulsion may be furtherdiluted with aliphatic or aromatic hydrocarbon solvent, preferablypentane or toluene.

[0094] In general, the Group 14 and Group 16 containing oil or amorphoussolid, preferably a siloxane, and the catalyst compound are combined inany useful weight ratio of weight siloxane:weight catalyst. Preferably,the weight ratio of weight siloxane:weight catalyst is between about1:10 to 100:1 preferably between about 1:1 and about 70:1, morepreferably between about 1:1 and about 50:1 and most preferably betweenabout 20:1 to about 40:1

[0095] In another embodiment, at least one catalyst compound, at leastone activator, and at least one Group 14 and Group 16 containing oil oramorphous solid, as described above, are combined to form a mixture withthe mixture being heated during activation to improve homogeneity. Themixture is heated to between about 30° C. and about 250° C., morepreferably between about 40° C. and about 1001C and even more preferablybetween about 50° C. and about 70° C.

[0096] In another embodiment, the catalyst of the invention has aspecific activity of between about 1 to 100,000,000 g/mmol·atm·h, morepreferably between about 10 and 100,000 g/mmol·atm·h, more preferablybetween about 25 and 50,000 g/mmol·atm·h.

[0097] Supports, Carriers and General Supporting Techniques

[0098] The above described catalyst and/or activator solutions oremulsions may be combined with one or more support materials or carriersusing one of the support methods well known in the art or as describedbelow to form a supported catalyst system. For example, the Group 14 andGroup 16 containing oil or amorphous solid catalyst and/or activatorsolution or emulsion may be deposited on, contacted with, vaporizedwith, bonded to, or incorporated within, adsorbed or absorbed in, or on,a support or carrier.

[0099] The terms “support” or “carrier”, for purposes of this patentspecification, are used interchangeably and are any support material,preferably a porous support material, including inorganic or organicsupport materials. Non-limiting examples of inorganic support materialsinclude inorganic oxides and inorganic chlorides. Other carriers includeresinous support materials such as polystyrene, functionalized orcrosslinked organic supports, such as polystyrene divinyl benzenepolyolefins or polymeric compounds, zeolites, talc, clays, or any otherorganic or inorganic support material and the like, or mixtures thereof.

[0100] The preferred carriers are inorganic oxides that include thoseGroup 2, 3, 4, 5, 13 or 14 metal oxides. The preferred supports includesilica, alumina, silica-alumina, magnesium chloride, and mixturesthereof. Other useful supports include magnesia, titania, zirconia,montmorillonite (EP-B 1 0 511 665), phyllosilicate, and the like. Also,combinations of these support materials may be used, for example,silica-chromium, silica-alumina, silica-titania and the like. Additionalsupport materials may include those porous acrylic polymers described inEP 0 767 184 B 1, which is incorporated herein by reference.

[0101] It is preferred that the carrier, most preferably an inorganicoxide, has a surface area in the range of from about 10 to about 700m²/g, pore volume in the range of from about 0.1 to about 4.0 cc/g andaverage particle size in the range of from about 5 to about 500 μm. Morepreferably, the surface area of the carrier is in the range of fromabout 50 to about 500 m²/g, pore volume of from about 0.5 to about 3.5cc/g and average particle size of from about 10 to about 200 μm. Mostpreferably the surface area of the carrier is in the range is from about100 to about 400 m²/g, pore volume from about 0.8 to about 3.0 cc/g andaverage particle size is from about 5 to about 100 μm. The average poresize of the carrier of the invention typically has pore size in therange of from 10 to 1000 Å, preferably 50 to about 500 Å, and mostpreferably 75 to about 350 Å.

[0102] Examples of supporting bulky ligand metallocene-type catalystsystems, which may be used to support the catalyst and/or activatorsolutions or emulsions of the invention, are described in U.S. Pat. Nos.4,701,432, 4,808,561, 4,912,075, 4,925,821, 4,937,217, 5,008,228,5,238,892, 5,240,894, 5,332,706, 5,346,925, 5,422,325, 5,466,649,5,466,766, 5,468,702, 5,529,965, 5,554,704, 5,629,253, 5,639,835,5,625,015, 5,643,847, 5,665,665, 5,698,487, 5,714,424, 5,723,400,5,723,402, 5,731,261, 5,759,940, 5,767,032, 5,770,664, 5,846,895 and5,939,348 and U.S. application Ser. Nos. 271,598 filed Jul. 7, 1994 and788,736 filed Jan. 23, 1997 and PCT publications WO 95/32995, WO95/14044, WO 96/06187 and WO 97/02297, and EP-B1-0 685 494 all of whichare herein fully incorporated by reference.

[0103] There are various other methods in the art for supporting thepolymerization catalyst solutions or emulsions of the invention. Forexample, the bulky ligand metallocene-type catalyst compound of theinvention may contain a polymer bound ligand as described in U.S. Pat.Nos. 5,473,202 and 5,770,755, which is herein fully incorporated byreference; the bulky ligand metallocene-type catalyst system of theinvention may be spray dried as described in U.S. Pat. No. 5,648,310,which is herein fully incorporated by reference; the support used withthe bulky ligand metallocene-type catalyst system of the invention maybe functionalized as described in European publication EP-A-0 802 203,which is herein fully incorporated by reference, or at least onesubstituent or leaving group may be selected as described in U.S. Pat.No. 5,688,880, which is herein fully incorporated by reference.

[0104] In another embodiment, an antistatic agent or surface modifier,that is used in the preparation of the supported catalyst system asdescribed in PCT publication WO 96/11960, which is herein fullyincorporated by reference, may be used with the Group 14 and Group 16containing oil or amorphous solid catalyst and/or activator solutions oremulsions of the invention, The catalyst systems of the invention can beprepared in the presence of an olefin, for example hexene-1.

[0105] In another embodiment, catalyst containing emulsions or solutionsof the invention can be combined with a carboxylic acid salt of a metalester, for example aluminum carboxylates such as aluminum mono, di- andtri- stearates, aluminum octoates, oleates and cyclohexylbutyrates, asdescribed in U.S. application Ser. No. 09/113,216, filed Jul. 10, 1998.

[0106] A preferred method for producing a supported bulky ligandmetallocene-type catalyst system, which maybe used to support thecatalyst and/or activator solutions or emulsions of the invention, isdescribed below, and is described in U.S. Application Serial Nos.265,533, filed Jun. 24, 1994 and 265,532, filed Jun. 24, 1994 and PCTpublications WO 96/00245 and WO 96/00243 both published Jan. 4, 1996,all of which are herein fully incorporated by reference. In thispreferred method, the catalyst compound is slurried in a liquid and witha Group 14 and Group 16 containing oil or amorphous solid to form acatalyst solution or emulsion. A separate solution is formed containingan activator and a liquid. The liquid may be any compatible solvent orother liquid capable of forming a solution or the like with the catalystcompounds and/or activator. In the most preferred embodiment the liquidis a cyclic aliphatic or aromatic hydrocarbon, most preferably toluene.The catalyst compound and activator solutions are mixed together heatedand added to a heated porous support or a heated porous support is addedto the solutions such that the total volume of the bulky ligandmetallocene-type catalyst compound solution and the activator solutionor the bulky ligand metallocene-type catalyst compound and activatorsolution is less than four times the pore volume of the porous support,more preferably less than three times, even more preferably less thantwo times; preferred ranges being from 1.1 times to 3.5 times range andmost preferably in the 1.2 to 3 times range.

[0107] Procedures for measuring the total pore volume of a poroussupport are well known in the art. Details of one of these procedures isdiscussed in Volume 1, Experimental Methods in Catalytic Research(Academic Press, 1968) (specifically see pages 67-96). This preferredprocedure involves the use of a classical BET apparatus for nitrogenabsorption. Another method well known in the art is described in Innes,Total Porosity and Particle Density ofFluid Catalysts By LiquidTitration, Vol. 28, No. 3, Analytical Chemistry 332-334 (March, 1956).

[0108] Polymerization Process

[0109] The Group 14 and Group 16 containing oil or amorphous solidcontaining catalyst compositions or systems of the invention describedabove are suitable for use in any prepolymerization and/orpolymerization process over a wide range of temperatures and pressures.The temperatures may be in the range of from −60° C. to about 280° C.,preferably from 50° C. to about 200° C., and the pressures employed maybe in the range from 1 atmosphere to about 500 atmospheres or higher.

[0110] Polymerization processes include solution, gas phase, slurryphase and a high pressure process or a combination thereof. Preferred isa gas phase or slurry phase polymerization of one or more olefins atleast one of which is ethylene or propylene.

[0111] In one embodiment, the process of this invention is directedtoward a solution, high pressure, slurry or gas phase polymerizationprocess of one or more olefin monomers having from 2 to 30 carbon atoms,preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbonatoms. The invention is particularly well suited to the polymerizationof two or more olefin monomers of ethylene, propylene, butene-1,pentene-1,4-methyl-pentene-1, hexene-1, octene-1 and decene-1.

[0112] Other monomers useful in the polymerization process of theinvention include ethylenically unsaturated monomers, diolefins having 4to 18 carbon atoms, conjugated or nonconjugated dienes, polyenes, vinylmonomers and cyclic olefins. Non-limiting monomers useful in theinvention may include norbornene, norbornadiene, isobutylene, isoprene,vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidenenorbornene, dicyclopentadiene and cyclopentene.

[0113] In the most preferred embodiment of the process of the invention,a copolymer of ethylene is produced, where with ethylene, a comonomerhaving at least one alpha-olefin having from 4 to 15 carbon atoms,preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8carbon atoms, is polymerized in a polymerization process.

[0114] In another embodiment of the process of the invention, ethyleneor propylene is polymerized with at least two different comonomers,optionally one of which may be a diene, to form a terpolymer.

[0115] In one embodiment, the invention is directed to a polymerizationprocess for polymerizing propylene alone or with one or more othermonomers including ethylene, and/or other olefins having from 4 to 12carbon atoms. Polypropylene polymers may be produced using theparticularly bridged bulky ligand metallocene-type catalysts asdescribed in U.S. Pat. Nos. 5,296,434 and 5,278,264, both of which areherein incorporated by reference.

[0116] Typically in a gas phase polymerization process a continuouscycle is employed where in one part of the cycle of a reactor system, acycling gas stream, otherwise known as a recycle stream or fluidizingmedium, is heated in the reactor by the heat of polymerization. Thisheat is removed from the recycle composition in another part of thecycle by a cooling system external to the reactor. Generally, in a gasfluidized bed process for producing polymers, a gaseous streamcontaining one or more monomers is continuously cycled through afluidized bed in the presence of a catalyst under reactive conditions.The gaseous stream is withdrawn from the fluidized bed and recycled backinto the reactor. Simultaneously, polymer product is withdrawn from thereactor and fresh monomer is added to replace the polymerized monomer.(See for example U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670,5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999,5,616,661 and 5,668,228, all of which are fully incorporated herein byreference.)

[0117] The reactor pressure in a gas phase process may vary from about100 psig (690 kPa) to about 500 psig (3448 kPa), preferably in the rangeof from about 200 psig (1379 kPa) to about 400 psig (2759 kPa), morepreferably in the range of from about 250 psig (1724 kPa) to about 350psig (2414 kPa).

[0118] The reactor temperature in a gas phase process may vary fromabout 30° C. to about 120° C., preferably from about 60° C. to about115° C., more preferably in the range of from about 70° C. to 110° C.,and most preferably in the range of from about 70° C. to about 95° C.

[0119] Other gas phase processes contemplated by the process of theinvention include series or multistage polymerization processes. Alsogas phase processes contemplated by the invention include thosedescribed in U.S. Pat. Nos. 5,627,242, 5,665,818 and 5,677,375, andEuropean publications EP-A-0 794 200 EP-B1-0 649 992, EP-A-0 802 202 andEP-B-634 421 all of which are herein fully incorporated by reference.

[0120] In a preferred embodiment, the reactor utilized in the presentinvention is capable and the process of the invention is producinggreater than 500 lbs of polymer per hour (227 Kg/hr) to about 200,000lbs/hr (90,900 Kg/hr) or higher of polymer, preferably greater than 1000lbs/hr (455 Kg/hr), more preferably greater than 10,000 lbs/hr (4540Kg/hr), even more preferably greater than 25,000 lbs/hr (11,300 Kg/hr),still more preferably greater than 35,000 lbs/hr (15,900 Kg/hr), stilleven more preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and mostpreferably greater than 65,000 lbs/hr (29,000 Kg/hr) to greater than100,000 lbs/hr (45,500 Kg/hr).

[0121] A slurry polymerization process generally uses pressures in therange of from about 1 to about 50 atmospheres and even greater andtemperatures in the range of 0° C to about 120° C. In a slurrypolymerization, a suspension of solid, particulate polymer is formed ina liquid polymerization diluent medium to which ethylene and comonomersand often hydrogen along with catalyst are added. The suspensionincluding diluent is intermittently or continuously removed from thereactor where the volatile components are separated from the polymer andrecycled, optionally after a distillation, to the reactor. The liquiddiluent employed in the polymerization medium is typically an alkanehaving from 3 to 7 carbon atoms, preferably a branched alkane. Themedium employed should be liquid under the conditions of polymerizationand relatively inert. When a propane medium is used the process must beoperated above the reaction diluent critical temperature and pressure.Preferably, a hexane or an isobutane medium is employed.

[0122] A preferred polymerization technique of the invention is referredto as a particle form polymerization, or a slurry process where thetemperature is kept below the temperature at which the polymer goes intosolution. Such technique is well known in the art, and described in forinstance U.S. Pat. No. 3,248,179 which is fully incorporated herein byreference. Other slurry processes include those employing a loop reactorand those utilizing a plurality of stirred reactors in series, parallel,or combinations thereof. Non-limiting examples of slurry processesinclude continuous loop or stirred tank processes. Also, other examplesof slurry processes are described in U.S. Pat. No. 4,613,484, which isherein fully incorporated by reference.

[0123] In an embodiment the reactor used in the slurry process of theinvention is capable of and the process of the invention is producinggreater than 2000 lbs of polymer per hour (907 Kg/hr), more preferablygreater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than10,000 lbs/hr (4540 Kg/hr). In another embodiment the slurry reactorused in the process of the invention is producing greater than 15,000lbs of polymer per hour (6804 Kg/hr), preferably greater than 25,000lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

[0124] Examples of solution processes, where the siloxane catalystand/or activator solutions or emulsions of the invention may beutilized, are described in U.S. Pat. Nos. 4,271,060, 5,001,205,5,236,998 and 5,589,555, which are fully incorporated herein byreference.

[0125] A preferred process of the invention is where the process isoperated in the presence of a bulky ligand metallocene-type catalystsystem of the invention and in the absence of or essentially free of anyscavengers, such as triethylaluminum, trimethylaluminum,tri-isobutylaluminum and tri-n-hexylaluminum and diethyl aluminumchloride, dibutyl zinc and the like. This preferred process is describedin PCT publication WO 96/08520 and U.S. Pat. No. 5,712,352 and5,763,543, which are herein fully incorporated by reference.

[0126] In one embodiment of the invention, olefin(s), preferably C₂ toC₃₀ olefin(s) or alpha-olefin(s), preferably ethylene or propylene orcombinations thereof are prepolymerized in the presence of the catalystsolution or emulsion of the invention prior to the main polymerization.The prepolymerization can be carried out batchwise or continuously ingas, solution or slurry phase including at elevated pressures. Theprepolymerization can take place with any olefin monomer or combinationand/or in the presence of any molecular weight controlling agent such ashydrogen. For examples of prepolymerization procedures, see U.S. Pat.Nos. 4,748,221, 4,789,359, 4,923,833, 4,921,825, 5,283,278 and 5,705,578and European publication EP-B-0279 863 and PCT Publication WO 97/44371all of which are herein fully incorporated by reference.

[0127] Polymer Products

[0128] The polymers produced by the process of the invention can be usedin a wide variety of products and end-use applications. The polymersproduced by the process of the invention include linear low densitypolyethylene, elastomers, plastomers, high density polyethylenes, mediumdensity polyethylenes, low density polyethylenes, polypropylene andpolypropylene copolymers.

[0129] The polymers, typically ethylene based polymers, have a densityin the range of from 0.86 g/cc to 0.97 g/cc, preferably in the range offrom 0.88 g/cc to 0.965 g/cc, more preferably in the range of from 0.900g/cc to 0.96 g/cc, even more preferably in the range of from 0.905 g/ccto 0.95 g/cc, yet even more preferably in the range from 0.910 g/cc to0.940 g/cc, and most preferably greater than 0.915 g/cc, preferablygreater than 0.920 g/cc, and most preferably greater than 0.925 g/cc.Density is measured in accordance with ASTM-D-1238.

[0130] The polymers produced by the process of the invention typicallyhave a molecular weight distribution, a weight average molecular weightto number average molecular weight (M_(w)/M_(n)) of greater than 1 toabout 40, preferably greater than 1.5 to about 15, more preferablygreater than 2 to about 10, most preferably greater than about 2.0 toabout 8.

[0131] Also, the polymers of the invention typically have a narrowcomposition distribution as measured by Composition Distribution BreadthIndex (CDBI). Further details of determining the CDBI of a copolymer areknown to those skilled in the art. See, for example, PCT PatentApplication WO 93/03093, published Feb. 18, 1993, which is fullyincorporated herein by reference.

[0132] The bulky ligand metallocene-type catalyzed polymers of theinvention in one embodiment have CDBI's generally in the range ofgreater than 50% to 100%, preferably 99%, preferably in the range of 55%to 85%, and more preferably 60% to 80%, even more preferably greaterthan 60%, still even more preferably greater than 65%.

[0133] In another embodiment, polymers produced using a bulky ligandmetallocene-type catalyst system of the invention have a CDBI less than50%, more preferably less than 40%, and most preferably less than 30%.

[0134] The polymers of the present invention in one embodiment have amelt index (MI) or (I₂) as measured by ASTM-D-1238-E in the range offrom less than 0.01 dg/min to 1000 dg/min, more preferably from aboutless than 0.01 dg/min to about 100 dg/min, even more preferably fromabout 0.1 dg/min to about 50 dg/min, and most preferably from about 0.1dg/min to about 10 dg/min.

[0135] The polymers of the invention in an embodiment have a melt indexratio (I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of about 5 to lessthan about 2500, preferably about 15 to about 250, more preferably about10 to about 25, more preferably from about 15 to about 25.

[0136] The polymers of the invention in a preferred embodiment have amelt index ratio (I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of frompreferably greater than 10, more preferably greater than 30, even morepreferably greater that 40, still even more preferably greater than 50and most preferably greater than 65. In an embodiment, the polymer ofthe invention may have a narrow molecular weight distribution and abroad composition distribution or vice-versa, and may be those polymersdescribed in U.S. Pat. No. 5,798,427 incorporated herein by reference.

[0137] In yet another embodiment, propylene based polymers are producedin the process of the invention. These polymers include atacticpolypropylene, isotactic polypropylene, hemi-isotactic and syndiotacticpolypropylene. Other propylene polymers include propylene block orimpact copolymers. Propylene polymers of these types are well known inthe art see for example U.S. Pat. Nos. 4,794,096, 3,248,455, 4,376,851,5,036,034 and 5,459,117, all of which are herein incorporated byreference.

[0138] The polymers of the invention may be blended and/or coextrudedwith any other polymer. Non-limiting examples of other polymers includelinear low density polyethylenes produced via conventional Ziegler-Nattaand/or bulky ligand metallocene-type catalysis, elastomers, plastomers,high pressure low density polyethylene, high density polyethylenes,polypropylenes and the like.

[0139] Polymers produced by the process of the invention and blendsthereof are useful in such forming operations as film, sheet, and fiberextrusion and co-extrusion as well as blow molding, injection moldingand rotary molding. Films include blown or cast films formed bycoextrusion or by lamination useful as shrink film, cling film, stretchfilm, sealing films, oriented films, snack packaging, heavy duty bags,grocery sacks, baked and frozen food packaging, medical packaging,industrial liners, membranes, etc. in food-contact and non-food contactapplications. Fibers include melt spinning, solution spinning and meltblown fiber operations for use in woven or non-woven form to makefilters, diaper fabrics, medical garments, geotextiles, etc. Extrudedarticles include medical tubing, wire and cable coatings, geomembranes,and pond liners. Molded articles include single and multi-layeredconstructions in the form of bottles, tanks, large hollow articles,rigid food containers and toys, etc.

EXAMPLES

[0140] In order to provide a better understanding of the presentinvention including representative advantages thereof, the followingexamples of catalyst compositions of the invention and theirpolymerization results, are offered.

[0141] All polymerizations were performed in a 2.2 L Autoclave EngineersZipperclave reactor. The ethylene feed was passed through a 1 L Labdlearpurification bed and a 1 L 3 Åmolecular sieve bed. The isobutane diluentwas fed from 5 gallon tanks and passed through a 2.2 L Labclearpurification bed. Prepurified hexene was obtained from in-housesuppliers. Pentane and toulene were obtained pre-dried from Aldrich,then degassed and stored over molecular sieves in a drybox. All catalystpreparations were preformed in a nitrogen purged drybox.

[0142] Siloxanes were purchased from: Gelest Inc., Tullytown, Pa. Thestructures of those utilized appear below.

[0143] Standard Polymerization Technique

[0144] A 2.2 L zipperclave reactor was charged with 1.4 mL of a 25 wt %hexane solution of tri-n-octylaluminum (TNOA) then with 440 g ofisobutane. This mixture was treated with ˜200 psi (1379 kPa) ethylenefor 5 to 10 minutes then let back down to ˜80 psi (552 kPa). Thecatalyst was injected into the reactor with nitrogen, and the reactorwas brought to temperature (60 to 90° C.) with stirring. When the runtemperature stabilized data collection began with ethylene supply to thereactor at 125 psi (862 kPa) over solvent pressure. Standard run timewas 30 minutes. The reactor was vented and flushed with nitrogen thenopened to collect the product.

[0145] Exceptions to the normal run profile are noted in the examples.The average run temperature and pressure, and the polyme r yield,specific gravity and melt index, for each example, are provided in TableI.

Example 1

[0146] A 750 mg portion of a 54 wt % DMS-V31 solution in toluene wastreated with 45 mg of a 25 wt % TNOA. To this was added cyclopentadienyl(pentamethylcyclopentadienyl) zirconium dimethyl, (10 mg), thenN,N-dimethylanilinium tetra(perfluorophenyl)borate (25 mg). The orangesolution was heated with stirring to ˜60° C. for several minutes thendiluted with 1 ml toluene. The resulting homogeneous orange solution wasadded to 10 ml of pentane. Polymerization of ethylene with 0.3 ml of thedilute solution resulted in a yield of 73 g of polyethylene.

Example 2

[0147] A 760 mg portion of a 50 wt % DMS-V31 solution in toluene wastreated with 45 mg of a 25 wt % TNOA. A toluene (400 mg) solution of(N,N-dimesityl-N′-methyl-ethylenetriamine)ZrMe₂ (10 mg) was added to thesiloxane solution and treated with N,N-dimethylaniliniumtetra(perfluorophenyl)borate (18 mg). The mixture became dark orange andgas was evolved. The reaction was then heated with stirring to ˜60° C.for several minutes then diluted with 10 ml toluene. Polymerization ofethylene with 0.3 ml of the dilute solution resulted in a yield of 3 gof polyethylene.

Example 3

[0148] 350 mg of DMS-V31, 350 mg of toluene, and 36 mg of a 25 wt %solution in hexane of tri-n-octylaluminum were combined in a vial andmixed for 1 to 2 minutes at ˜60° C. A 10 mg portion ofbis(n-propylcyclopentadienyl)HfMe₂ was added with continued stirring andwarming followed by 22 mg of triphenylcarbeniumtetra(perfluorophenyl)borate. The mixture became dark yellow-orange.Stirring and heating continued for several minutes followed by additionof 1 ml toluene. This solution was mixed well then added to 10 mltoluene. Polymerization of ethylene with 0.3 ml of the dilute solutionyielded 11.7 g of polymer.

Example 4

[0149] 700 mg of a 50 wt % toluene solution of DMS-V31 and 36 mg of a 25wt % solution in hexane of tri-n-octylaluminum were combined in a vialand mixed for 1 to 2 minutes at ˜60° C. A 10 mg portion ofdimethylsilyl-bis(tetrahydroindenyl)ZrMe₂ was added with continuedstirring and warming followed by 24 mg of triphenylcarbeniumtetra(perfluorophenyl)borate. The mixture became dark yellow-orange.Stirring and heating continued for several minutes followed by additionof 1 ml toluene. This solution was mixed well then added to 10 mltoluene. Polymerization of ethylene with 0.3 ml of the dilute solutionyielded 110 g of polymer.

Example 5

[0150] 700 mg of a 50 wt % toluene solution of DMS-V31 and 36 mg of a 25wt % solution in hexane of tri-n-octylaluminum were combined in a vialand mixed for 1 to 2 minutes at ambient temperature. A 10 mg portion ofdimethylsilyl-bis(tetrahydroindenyl)ZrMe₂ was added with continuedstirring followed by 23 mg of triphenylcarbeniumtetra(perfluorophenyl)borate. The mixture became yellow. Stirringcontinued for several minutes followed by addition of 1 ml toluene. Thissolution was mixed well then added to 10 ml toluene. Polymerization ofethylene with 0.3 ml of the dilute solution yielded 100 g of polymer.

Example 6

[0151] 700 mg of a 50 wt % toluene solution of DES-T23 and 36 mg of a 25wt % solution in hexane of tri-n-octylaluminum were combined in a vialand mixed for 1 to 2 minutes at ˜60° C. A 10 mg portion ofcyclopentadienyl (pentamethylcyclopentadienyl) zirconium dimethyl, wasadded with continued stirring and warming followed by 25 mg ofN,N-dimethylanilinium tetra(perfluorophenyl)borate. The mixture becamedark yellow-orange and gas was evolved. Stirring and heating continuedfor several minutes followed by addition of 1 ml toluene. This solutionwas mixed well then added to 10 ml toluene. Polymerization of ethylenewith 0.3 ml of the dilute solution yielded 63 g of polymer.

Example 7

[0152] 350 mg of DMS-V52, 350 mg of toluene, and 36 mg of a 25 wt %solution in hexane of tri-n-octylaluminum were combined in a vial andmixed for 1-2 minutes at ˜60° C. A 10 mg portion ofdimethylsilyl-bis(tetrahydroindenyl)ZrMe₂ was added with continuedstirring and warming followed by 24 mg of triphenylcarbeniumtetra(perfluorophenyl)borate. The mixture became dark yellow-orange.Stirring and heating continued for several minutes followed by additionof 1 ml toluene. This solution was mixed well then added to 10 mltoluene. Polymerization of ethylene with 0.3 ml of the dilute solutionyielded 19.9 g of polymer.

Example 8

[0153] 700 mg of a 50 wt % toluene solution of DES-T23 and 36 mg of a 25wt % solution in hexane of tri-n-octylaluminum were combined in a vialand mixed for 1-2 minutes at ˜60° C. A 10 mg portion ofdimethylsilyl-bis(tetrahydroindenyl)ZrMe₂ was added with continuedstirring and warming followed by 25 mg of triphenylcarbeniumtetra(perfluorophenyl)borate. The mixture became dark yellow. Stirringand heating continued for several minutes followed by addition of 1 mltoluene. This solution was mixed well then added to 10 ml toluene.Polymerization of ethylene with 0.3 ml of the dilute solution yielded 60g of polymer.

Example 9

[0154] 700 mg of a 50 wt % toluene solution of DMS-V31 was combined witha 10 mg portion of dimethylsilyl-bis(tetrahydroindenyl)ZrMe₂ in a vialand mixed for 1-2 minutes at ˜60° C., followed by 25 mg oftriphenylcarbenium tetra(perfluorophenyl)borate. The mixture became darkyellow. Stirring and heating continued for several minutes followed byaddition of 1 ml toluene. This solution was mixed well then added to 10ml toluene. Polymerization of ethylene with 0.3 ml of the dilutesolution yielded 17.4 g of polymer.

Example 10

[0155] 700 mg of a 50 wt % toluene solution of DMS-V31 and 36 mg of a 25wt % solution in hexane of tri-n-octylaluminum were combined in a vialand mixed for 1-2 minutes at ˜60° C. A 10 mg portion ofdimethylsilyl-bis(tetrahydroindenyl)ZrMe₂ was added with continuedstirring and warming followed by 13 mg of tris(perfluorophenyl)borane.Stirring and heating continued for several minutes followed by additionof 1 ml toluene. This solution was mixed well then added to 10 mltoluene. Polymerization of ethylene with 0.3 ml of the dilute solutionyielded 30 g of polymer.

Example 11

[0156] 700 mg of a 50 wt % toluene solution of DMS-V31 and 36 mg of a 25wt % solution in hexane of tri-n-octylaluminum were combined in a vialand mixed for 1-2 minutes at ˜60° C. A 10 mg portion ofdimethylsilyl-bis(tetrahydroindenyl)ZrMe₂ was added with continuedstirring and warming followed by 25 mg of triphenylcarbeniumtetra(perfluorophenyl)borate. The mixture became dark yellow. Stirringand heating continued for several minutes followed by addition of 1 mltoluene. This solution was mixed well then added to 10 ml pentane.Polymerization of ethylene with 0.3 ml of the dilute solution yielded 15g of polymer.

Example 12

[0157] 175 mg of a 50 wt % toluene solution of DMS-V31 and 36 mg of a 25wt % solution in hexane of tri-n-octylaluminum were combined in a vialand mixed for 1-2 minutes at ˜60° C. A 0.2 ml portion of a 0.125Mtoluene solution of [1-(2-pyridyl) N-1-methylethyl][1-N-2,6diisopropylphenylamido] zirconium tribenzyl was added with continuedstirring and warming followed by 23 mg of triphenylcarbeniumtetra(perfluorophenyl)borate. Stirring and heating continued for severalminutes followed by addition of 1 ml toluene. This solution was mixedwell then added to 10 ml toluene. Polymerization of ethylene with 0.3 mlof the dilute solution yielded 18.8 g of polymer.

Example 13

[0158] 175 mg of a 50 wt % toluene solution of DMS-V31 and 36 mg of a 25wt % solution in hexane of tri-n-octylaluminum were combined in a vialand mixed for 1-2 minutes at ˜60° C. A 0.3 ml portion of a 0.08M toluenesolution of [1-(2-pyridyl) N-1-methylethyl][1-N-2,6diisopropylphenylamido] [2-methyl-1-phenyl-2-propoxy] zirconium dibenzylwas added with continued stirring and warming followed by 23 mg oftriphenylcarbenium tetra(perfluorophenyl)borate. Stirring and heatingcontinued for several minutes followed by addition of 1 ml toluene. Thissolution was mixed well then added to 10 ml toluene. Co-polymerizationof ethylene with hexene, with 0.3 ml of the dilute solution, yielded16.9 g of polymer.

Example 14

[0159] A 350 mg portion of a 50 wt % DMS-V31 in toluene was treated with36 mg of 25 wt % tri-n-octylaluminum in hexanes. A toluene (0.5 ml)solution of 12 mg of (N,N-dimesityl-N′-methyl-ethylenetriamine)ZrMe2 wasadded to the siloxane and treated with 23 mg of triphenylcarbeniumtetra(perfluorophenyl)borate. The mixture became dark orange. Thereaction was then stirred for several minutes then 0.5 ml of toluene wasadded. The solution was mixed further and then added to 10 ml toluene.Polymerization of ethylene with 0.3 ml of the dilute solution resultedin a yield of 16.3 g of polyethylene.

Example 15

[0160] A 700 mg portion of a 54 wt % DMS-V31 solution in toluene wastreated with 72 mg of a 25 wt % TNOA. cyclopentadienyl(pentamethylcyclopentadienyl) zirconium dichloride (10 mg), was addedand the mixture was warmed to ˜60° C. until the metallocene dissolved.At this point the solution was bright yellow. The metallocene wasactivated with 23 mg of triphenylcarbenium tetra(perfluorophenyl)borate.The orange solution was heated with stirring to ˜60° C. for severalminutes then diluted with 1 ml toluene. The resulting solution wasstirred with warming for several minutes with 1 ml toluene and mixedfurther. This solution was then added to 10 ml toluene. Polymerizationof ethylene with 0.3 ml of the dilute solution resulted in a yield of 10g of polyethylene.

Example 16

[0161] A 700 mg portion of a 54 wt % FMV-403 1 in toluene was treatedwith 73 mg of 25 wt % tri-n-octylaluminum in hexanes. Thepentamethylcyclopentadienyl (n-propyl-cyclopentadienyl) zirconiumdichloride (Cp*Cp^(n-pr)ZrCl₂) (11 mg), was added to the siloxane andmixed for several minutes. The solution was then treated with 23 mg oftriphenylcarbenium tetra(perfluorophenyl)borate. The reaction wasstirred for several minutes, then 1 ml of toluene was added. Thesolution was mixed further and then added to 10 ml toluene.Polymerization of ethylene with 0.3 ml of the dilute solution resultedin a yield of 29.4 g of polyethylene.

Example 17

[0162] A 350 mg portion of a 54 wt % FMV-403 1 in toluene was treatedwith 72 mg of 25 wt % tri-n-octylaluminum in hexanes.Dimethylsilyl-bis(tetrahydroindenyl)ZrMe₂ (11 mg) was added to thesiloxane and mixed for several minutes. The solution was then treatedwith 23 mg of triphenylcarbenium tetra(perfluorophenyl)borate. Thereaction was stirred for several minutes, then 1 ml of toluene wasadded. The solution was mixed further and then added to 10 ml toluene.Polymerization of ethylene with 0.3 ml of the dilute solution resultedin a yield of 33 g of polyethylene.

Example 18

[0163] A 700 mg portion of a 50 wt % DMS-V31 in toluene was treated with36 mg of 25 wt % tri-n-octylaluminum in hexanes. A toluene (0.5 ml)solution of 9 mg of (N,N-dimesityl-N′-methyl-ethylenetriamine)ZrMe₂ wasadded to the siloxane followed by a 4.5 mg portion ofdimethylsilyl-bis(tetrahydroindenyl)ZrMe₂. The mixture was then treatedwith 24 mg of triphenylcarbenium tetra(perfluorophenyl)borate. Thereaction was then stirred for several minutes then 0.5 ml of toluene wasadded. The solution was mixed further and then added to 10 ml toluene.Polymerization of ethylene with 0.3 ml of the dilute solution resultedin a yield of 76.5 g of polyethylene.

Example 19

[0164] A 11.9 g sample of silica dried at elevated temperatures wasmixed in toluene with 6.5 g of a 25 wt % hexanes solution oftriethylaluminum (TEAL) for 15 minutes. The silica was recovered byfiltration and dried in vacuuo. A 700 mg portion of a 50 wt % DES-T23 intoluene was treated with 46 mg of 25 wt % tri-n-octylaluminum inhexanes. cyclopentadienyl (pentamethylcyclopentadienyl) zirconiumdimethyl (10 mg), was added to the siloxane followed by 24 mg oftriphenylcarbenium tetra(perfluorophenyl)borate. The reaction wasstirred for several minutes then 1.4 ml of toluene was added. Thesolution was mixed further and then 0.5 g of the TEAL-treated silica wasadded and the mixture was stirred with a spatula. The solids were thendried in vacuuo. Polymerization of ethylene with 0.1 g of the finishedsolid resulted in a yield of 38.8 g of polyethylene. Note that thepretreatment of isobutane diluent with ethylene as described in thegeneral polymerization technique was not performed in this example.

Example 20

[0165] 500 mg ofFMV-4031 and 111 mg of a 25 wt % solution in hexaneoftri-n-octylaluminum were combined in a vial and mixed. A 32 mg portionof bis(n-propylcyclopentadienyl)HfMe₂ was added with continued stirringfollowed by 70 mg of triphenylcarbenium tetra(perfluorophenyl)borate.Stirring continued for several minutes followed by addition of 1 mltoluene. To this mixture was added silica (1 g) previously treated witha mixture of MAO and bis(n-propylcyclopentadienyl)ZrCl₂. The resultingsolids were mixed with a spatula and dried in vacuuo. Polymerization ofethylene with 0.1 g of the finished solids yielded 64.8 g of polymer.Note that the pretreatment of isobutane diluent with ethylene asdescribed in the general polymerization technique was not performed inthis example.

Example 21

[0166] 700 mg of FMV-4031 and 36 mg of a 25 wt % solution in hexane oftri-n-octylaluminum were combined in a vial and mixed. A 15 mg portionof (N,N′-2,6-diisopropylphenyl-ethylene-di-imine)NiBr₂ was added, atwhich point the solution became dark violet. After a few minutes ofmixing, 23 mg of triphenylcarbenium tetra(perfluorophenyl)borate wasadded. Stirring continued for several minutes followed by addition of 1ml toluene. The solution was mixed then added to 10 ml of toluene.Polymerization of ethylene with 0.3 ml of the dilute solution yielded0.50 g of polymer. TABLE I Average Flow Average Run Index Run PressureSpecific I₂₁ Example Temp. psi Polymer Activity (dg/ Number ° C. (kPa)Yield g g/mmol · atm · h min) 1 90 378 (2606) 73.0 25514 4.0 2 90 393(2710) 3.0 933 0.2 3 90 379 (2613) 11.7 4149 NF* 4 90 375 (2586) 11038547 2.2 5 90 373 (2572) 100 36323 — 6 90 376 (2592) 63.0 22526 3.5 790 381 (2627) 19.9 6749 5.5 8 90 376 (2592) 60.8 22925 5.0 9 90 376(2592) 17.4 6120 4.0 10 90 376 (2592) 30.6 10814 5.2 11 90 377 (2599)15.6 5470 3.6 12 90 377 (2599) 18.8 6584 0.6 13 90 376 (2592) 16.9 60012.6 14 61 376 (2592) 16.3 5691 NF* 15 90 375 (2586) 10.0 3546 13 16 90401 (2765) 29.4 8595 0.5 17 90 377 (2599) 33.1 11633 1.4 18 90 374(2579) 76.5 27508 3.1 19 90 378 (2606) 38.8 4636 4.5 20 90 378 (2606)64.8 1675 2.4 21 61 380 (2620) 0.50 100 —

[0167] While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For example, more than one siloxane maybe utilized to solubilize or emulsify more than one polymerizationcatalyst compound and/or more than one activator compound. For thisreason, then, reference should be made solely to the appended claims forpurposes of determining the true scope of the present invention.

I claim:
 1. A method of preparing a polymerization catalyst comprisingcombining a bulky-ligand metallocene or a Group 15 containingpolymerization catalyst with an alternating Group 14 and Group 16containing oil or amorphous solid to form a catalyst solution oremulsion; wherein the alternating group 14 and Group 16 atom containingoil or amorphous solid is represented by the formulae:T-M(R¹)₂-Q-(M(R²)₂-Q)_(n)-M(R¹)₂-T orT-M(R¹)₂-Q-(M(R²)₂-Q)_(n)-(M(R³)₂-Q)_(m)-Si(R¹)₂-T wherein each T, R¹,R², and R³ is independently selected from the group consisting ofhydride, alkyl, alkoxy, aryl, substituted aryl, cycloalkyl, substitutedcyclic alkyl, cyclic arylalkyl, substituted cyclic arylalkyl,heteroatom, vinyl, silyl, silyloxy, vinylsiloxy, haloaryl, haloalkyl, orvinylsilyl containing group; each M is independently an atom of Group 14of the periodic table; each Q is independently an atom of Group 16 ofthe periodic table; and wherein n and m independently an integer betweenabout 1 and 40,000.
 2. The method of claim 1, further comprisingcombining a scavenger.
 3. The method of claim 1, further comprisingcombining an activator composition.
 4. The method of claim 3, whereinthe activator composition is a stoichiometric activator.
 5. The methodof claim 1, further comprising heating the catalyst solution or emulsionduring activation.
 6. The method of claim 5, wherein the catalystsolution or emulsion is heated to between about 30° C. and about 250° C.7. The method of claim 5, wherein the catalyst solution or emulsion isheated to between about 40° C. and about 100° C.
 8. The method of claim1, wherein the weight ratio of oil or amorphous solid-to-weightpolymerization catalyst is between about 1:10 to 100:1.
 9. The method ofclaim 1, wherein the weight ratio of oil or amorphous solid-to-weightpolymerization catalyst is between 1:1 and about 70:1.
 10. The method ofclaim 1, wherein the catalyst solution or emulsion is further combinedwith a support or carrier.
 11. The method of claim 1, wherein a supportor carrier is absent from the catalyst solution or emulsion as used inpolymerizing olefins.
 12. A catalyst system comprising a bulky-ligandmetallocene or a Group 15 containing polymerization catalyst and analternating Group 14 and Group 16 atom containing oil or amorphoussolid; wherein the alternating group 14 and Group 16 atom containing oilor amorphous solid is represented by the formulae:T-M(R¹)₂-Q-(M(R²)₂-Q)_(n)-M(R¹)₂-T orT-M(R¹)₂-Q-(M(R²)₂-Q)_(n)-(M(R³)₂-Q)_(m)-Si(R¹)₂-T wherein each T, R¹,R², and R³ is independently selected from the group consisting ofhydride, alkyl, alkoxy, aryl, substituted aryl, cycloalkyl, substitutedcyclic alkyl, cyclic arylalkyl, substituted cyclic arylalkyl, vinyl,silyl, silyloxy, vinylsiloxy, haloaryl, haloalkyl, or vinylsilylcontaining group; each M is independently an atom of Group 14 of theperiodic table; each Q is independently an atom of Group 16 of theperiodic table; and wherein n and m independently an integer betweenabout 1 and 40,000.
 13. The catalyst system of claim 12, wherein Msilicon or germanium.
 14. The catalyst system of claim 12, wherein M issilicon an Q is oxygen.
 15. The catalyst system of claim 12, whereineach T is independently a methyl, ethyl or vinyl group.
 16. The catalystsystem of claim 12, wherein each R¹ and R² is independently a methyl orethyl group.
 17. The catalyst system of claim 12, wherein in each R³ isindependently a halogenated or non-halogenated methyl, ethyl, propyl orphenyl group.
 18. The catalyst system of claim 12, wherein the Group 14and Group 16 non-crystalline compound comprises a siloxane oil orcombination of siloxanes oils having a viscosity of between about 100cSt and about 500,000 cSt and a number average molecular weight betweenabout 60 and about 100,000.
 19. The catalyst system of claim 12, whereinthe catalyst system further comprises an activator.
 20. The catalystsystem of claim 19, wherein the activator is a stoichiometric activator.21. The catalyst system of claim 12, wherein the stoichiometricactivator is represented by the formula: (L-H)_(d) ⁺(A^(d−)) wherein L′is an neutral Lewis base; H is hydrogen; (L-H)⁺is a Bronsted acid;A^(d—)is a non-coordinating anion having the charge d−; and d is aninteger from 1 to
 3. 22. The catalyst system of claim 12, wherein theactivator is selected from a group consisting of tri(n-butyl)ammoniumtetrakis(pentafluorophenyl) borate, a trisperfluorophenyl boronmetalloid precursor or a trisperfluoronaphtyl boron metalloid precursor,polyhalogenated heteroborane anions or a combination thereof.
 23. Thecatalyst system of claim 12, wherein the catalyst system is a solutionor emulsion.
 24. The catalyst system of claim 12, wherein the catalystsystem is combined with one or more supports or carriers.
 25. Thecatalyst system of claim 12, wherein a support or carrier is absent fromthe catalyst solution or emulsion as used in polymerizing olefins. 26.The catalyst system of claim 12, wherein the weight ratio of oil oramorphous solid-to-weight polymerization catalyst is between about 1:10to 100:1.
 27. The catalyst system of claim 12, wherein the weight ratioof oil or amorphous solid-to-weight polymerization catalyst is between1:1 and about 70:1.